Bis(propan-2-yl) [(2S,3S)-2-hydr­oxy-3-nitro­butan-2-yl]phospho­nate

Abstract

In the title compound, C₁₀H₂₂NO₆P, a staggered conformation is found when the mol­ecule is viewed down the central P—C bond, with the oxo and hydr­oxy groups gauche to each other. The crystal structure features supra­molecular chains of helical topology propagating along the b axis, mediated by O—H⋯O hydrogen bonds.

Related literature

For background to the enanti­oselective nitro­aldol reaction of α-ketophospho­nates and nitro­methane and for the synthesis, see: Mandal et al. (2007 ▶).

Experimental

Crystal data

• C₁₀H₂₂NO₆P

• M _r = 283.26

• Orthorhombic,

• a = 7.8620 (16) Å

• b = 11.369 (2) Å

• c = 16.920 (3) Å

• V = 1512.4 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.20 mm⁻¹

• T = 173 K

• 0.32 × 0.10 × 0.05 mm

Data collection

• Rigaku AFC12/SATURN724 diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.884, T _max = 1

• 13441 measured reflections

• 3072 independent reflections

• 3020 reflections with I > 2σ(I)

• R _int = 0.089

• Standard reflections: 0

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.105

• S = 1.07

• 3072 reflections

• 166 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1272 Friedel pairs

• Flack parameter: 0.05 (11)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4o⋯O1i	0.84	1.90	2.7289 (19)	172

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound, (I), was investigated as a part of previous studies on the enantioselective nitroaldol reaction of α-ketophosphonates and nitromethane for the synthesis of optically active α-hydroxy-β-nitrophosphonates (Mandal et al., 2007). The crystal structure analysis of (I), Fig. 1, shows a staggered conformation when the molecule is viewed down the P–C7 axis in which the oxo and hydroxy groups are gauche to each other. The presence of O–H···O hydrogen bonding formed between the hydroxy-O4—H and O═P atoms leads to the formation of supramolecular chains along the b axis, Fig. 2 and Table 1.

Experimental

The title compound was prepared as described in the literature (Mandal et al., 2007).

Refinement

The C-bound H atoms were geometrically placed (C—H = 0.98–1.00 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C). The methyl H-atoms were rotated to fit the electron density. The O–H H atom was located from a difference map and refined with O–H = 0.840±0.001 Å, and with U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

Molecular structure of (I), showing displacement ellipsoids at the 35% probability level.

Fig. 2.

Supramolecular chain along the b axis in (I) mediated by O–H···O (orange dashed lines) hydrogen bonding. Colour scheme: P, olive; O, red; N, blue; C, grey; and H, green.

Crystal data

C10H22NO6P	F(000) = 608
Mr = 283.26	Dx = 1.244 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2308 reflections
a = 7.8620 (16) Å	θ = 4.0–30.1°
b = 11.369 (2) Å	µ = 0.20 mm−1
c = 16.920 (3) Å	T = 173 K
V = 1512.4 (5) Å3	Block, pale-yellow
Z = 4	0.32 × 0.10 × 0.05 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer	3072 independent reflections
Radiation source: fine-focus sealed tube	3020 reflections with I > 2σ(I)
graphite	Rint = 0.089
ω scans	θmax = 26.5°, θmin = 4.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→8
Tmin = 0.884, Tmax = 1	k = −13→14
13441 measured reflections	l = −21→20

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0497P)2 + 0.2822P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3072 reflections	Δρmax = 0.19 e Å−3
166 parameters	Δρmin = −0.25 e Å−3
1 restraint	Absolute structure: Flack (1983), 1272 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.63065 (6)	0.29509 (4)	0.74005 (3)	0.03236 (14)
O1	0.51586 (18)	0.19464 (11)	0.75316 (9)	0.0416 (3)
O2	0.80539 (18)	0.26553 (13)	0.70112 (9)	0.0415 (3)
O3	0.67933 (17)	0.36408 (13)	0.81677 (8)	0.0383 (3)
O4	0.41385 (17)	0.46364 (12)	0.71762 (9)	0.0400 (3)
H4O	0.4448	0.5337	0.7241	0.060*
O5	0.3878 (4)	0.49342 (19)	0.51776 (13)	0.0848 (7)
O6	0.1751 (3)	0.4227 (2)	0.58457 (14)	0.0861 (7)
N1	0.3262 (3)	0.4256 (2)	0.56573 (14)	0.0608 (6)
C1	0.9313 (3)	0.18894 (18)	0.74033 (13)	0.0438 (5)
H1	0.8736	0.1412	0.7821	0.053*
C2	0.9985 (4)	0.1089 (3)	0.67718 (17)	0.0706 (8)
H2A	0.9051	0.0617	0.6556	0.106*
H2B	1.0849	0.0567	0.6998	0.106*
H2C	1.0495	0.1560	0.6348	0.106*
C3	1.0653 (3)	0.2668 (2)	0.7782 (2)	0.0656 (8)
H3A	1.0121	0.3162	0.8187	0.098*
H3B	1.1173	0.3168	0.7377	0.098*
H3C	1.1530	0.2175	0.8026	0.098*
C4	0.5800 (3)	0.3614 (2)	0.89018 (13)	0.0551 (6)
H4	0.4659	0.3254	0.8803	0.066*
C5	0.5601 (6)	0.4848 (3)	0.91703 (18)	0.0879 (11)
H5A	0.4970	0.5295	0.8771	0.132*
H5B	0.6726	0.5202	0.9246	0.132*
H5C	0.4976	0.4862	0.9671	0.132*
C6	0.6764 (7)	0.2898 (3)	0.94900 (18)	0.1056 (15)
H6A	0.6874	0.2089	0.9296	0.158*
H6B	0.6152	0.2896	0.9995	0.158*
H6C	0.7897	0.3238	0.9565	0.158*
C7	0.5409 (2)	0.40550 (16)	0.67209 (11)	0.0336 (4)
C8	0.4436 (3)	0.33911 (18)	0.60636 (12)	0.0419 (5)
H8	0.3722	0.2770	0.6318	0.050*
C9	0.5556 (4)	0.2804 (2)	0.54440 (13)	0.0558 (6)
H9A	0.4838	0.2406	0.5053	0.084*
H9B	0.6299	0.2227	0.5700	0.084*
H9C	0.6251	0.3401	0.5179	0.084*
C10	0.6767 (3)	0.49079 (18)	0.64308 (14)	0.0430 (5)
H10A	0.7312	0.5287	0.6885	0.065*
H10B	0.6239	0.5509	0.6095	0.065*
H10C	0.7623	0.4477	0.6125	0.065*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
P1	0.0303 (2)	0.0284 (2)	0.0384 (2)	0.00159 (18)	0.00078 (17)	0.00062 (19)
O1	0.0432 (7)	0.0284 (6)	0.0532 (8)	−0.0023 (5)	−0.0002 (6)	0.0044 (7)
O2	0.0357 (7)	0.0454 (8)	0.0435 (7)	0.0140 (6)	0.0051 (6)	0.0031 (6)
O3	0.0365 (7)	0.0426 (7)	0.0359 (7)	−0.0048 (6)	0.0024 (5)	−0.0017 (6)
O4	0.0342 (7)	0.0316 (7)	0.0541 (8)	0.0031 (6)	0.0021 (6)	−0.0080 (6)
O5	0.1205 (19)	0.0631 (12)	0.0708 (13)	0.0063 (14)	−0.0288 (14)	0.0171 (10)
O6	0.0593 (13)	0.1078 (17)	0.0912 (16)	0.0212 (13)	−0.0342 (12)	−0.0093 (14)
N1	0.0736 (16)	0.0513 (12)	0.0576 (12)	0.0103 (11)	−0.0261 (11)	−0.0073 (11)
C1	0.0408 (10)	0.0399 (11)	0.0507 (11)	0.0124 (8)	−0.0022 (9)	0.0007 (10)
C2	0.0768 (19)	0.0698 (17)	0.0650 (16)	0.0410 (16)	−0.0121 (14)	−0.0150 (14)
C3	0.0423 (12)	0.0584 (15)	0.096 (2)	0.0113 (11)	−0.0130 (13)	−0.0103 (14)
C4	0.0576 (14)	0.0725 (16)	0.0351 (10)	−0.0157 (12)	0.0104 (9)	−0.0010 (10)
C5	0.128 (3)	0.085 (2)	0.0507 (15)	0.038 (2)	0.0216 (17)	−0.0070 (15)
C6	0.189 (5)	0.081 (2)	0.0471 (15)	0.029 (3)	0.004 (2)	0.0180 (16)
C7	0.0344 (9)	0.0283 (8)	0.0383 (9)	0.0022 (7)	−0.0010 (8)	−0.0021 (8)
C8	0.0498 (12)	0.0332 (9)	0.0428 (10)	0.0031 (9)	−0.0088 (9)	−0.0032 (9)
C9	0.0772 (17)	0.0502 (13)	0.0399 (11)	0.0049 (13)	0.0000 (11)	−0.0097 (10)
C10	0.0451 (11)	0.0334 (10)	0.0506 (12)	−0.0024 (9)	0.0042 (9)	0.0032 (9)

Geometric parameters (Å, °)

P1—O1	1.4723 (14)	C4—C5	1.483 (4)
P1—O2	1.5602 (14)	C4—C6	1.492 (4)
P1—O3	1.5643 (15)	C4—H4	1.0000
P1—C7	1.8428 (19)	C5—H5A	0.9800
O2—C1	1.476 (2)	C5—H5B	0.9800
O3—C4	1.467 (2)	C5—H5C	0.9800
O4—C7	1.424 (2)	C6—H6A	0.9800
O4—H4O	0.8400	C6—H6B	0.9800
O5—N1	1.219 (3)	C6—H6C	0.9800
O6—N1	1.230 (4)	C7—C10	1.524 (3)
N1—C8	1.514 (3)	C7—C8	1.546 (3)
C1—C2	1.500 (3)	C8—C9	1.523 (3)
C1—C3	1.517 (3)	C8—H8	1.0000
C1—H1	1.0000	C9—H9A	0.9800
C2—H2A	0.9800	C9—H9B	0.9800
C2—H2B	0.9800	C9—H9C	0.9800
C2—H2C	0.9800	C10—H10A	0.9800
C3—H3A	0.9800	C10—H10B	0.9800
C3—H3B	0.9800	C10—H10C	0.9800
C3—H3C	0.9800
O1—P1—O2	115.86 (9)	C4—C5—H5A	109.5
O1—P1—O3	114.44 (9)	C4—C5—H5B	109.5
O2—P1—O3	104.06 (8)	H5A—C5—H5B	109.5
O1—P1—C7	112.80 (9)	C4—C5—H5C	109.5
O2—P1—C7	102.75 (8)	H5A—C5—H5C	109.5
O3—P1—C7	105.67 (8)	H5B—C5—H5C	109.5
C1—O2—P1	121.86 (13)	C4—C6—H6A	109.5
C4—O3—P1	124.17 (14)	C4—C6—H6B	109.5
C7—O4—H4O	108.0	H6A—C6—H6B	109.5
O5—N1—O6	124.9 (3)	C4—C6—H6C	109.5
O5—N1—C8	118.1 (2)	H6A—C6—H6C	109.5
O6—N1—C8	117.0 (2)	H6B—C6—H6C	109.5
O2—C1—C2	105.91 (18)	O4—C7—C10	111.74 (15)
O2—C1—C3	108.14 (17)	O4—C7—C8	105.60 (16)
C2—C1—C3	114.2 (2)	C10—C7—C8	115.18 (18)
O2—C1—H1	109.5	O4—C7—P1	104.31 (12)
C2—C1—H1	109.5	C10—C7—P1	111.47 (14)
C3—C1—H1	109.5	C8—C7—P1	107.80 (13)
C1—C2—H2A	109.5	N1—C8—C9	108.94 (19)
C1—C2—H2B	109.5	N1—C8—C7	108.11 (16)
H2A—C2—H2B	109.5	C9—C8—C7	115.0 (2)
C1—C2—H2C	109.5	N1—C8—H8	108.2
H2A—C2—H2C	109.5	C9—C8—H8	108.2
H2B—C2—H2C	109.5	C7—C8—H8	108.2
C1—C3—H3A	109.5	C8—C9—H9A	109.5
C1—C3—H3B	109.5	C8—C9—H9B	109.5
H3A—C3—H3B	109.5	H9A—C9—H9B	109.5
C1—C3—H3C	109.5	C8—C9—H9C	109.5
H3A—C3—H3C	109.5	H9A—C9—H9C	109.5
H3B—C3—H3C	109.5	H9B—C9—H9C	109.5
O3—C4—C5	107.2 (2)	C7—C10—H10A	109.5
O3—C4—C6	107.8 (2)	C7—C10—H10B	109.5
C5—C4—C6	111.4 (3)	H10A—C10—H10B	109.5
O3—C4—H4	110.1	C7—C10—H10C	109.5
C5—C4—H4	110.1	H10A—C10—H10C	109.5
C6—C4—H4	110.1	H10B—C10—H10C	109.5
O1—P1—O2—C1	−63.20 (17)	O3—P1—C7—C10	68.93 (15)
O3—P1—O2—C1	63.34 (17)	O1—P1—C7—C8	−37.99 (17)
C7—P1—O2—C1	173.35 (15)	O2—P1—C7—C8	87.48 (15)
O1—P1—O3—C4	−21.1 (2)	O3—P1—C7—C8	−163.73 (13)
O2—P1—O3—C4	−148.58 (17)	O5—N1—C8—C9	−47.5 (3)
C7—P1—O3—C4	103.58 (19)	O6—N1—C8—C9	133.2 (2)
P1—O2—C1—C2	136.98 (19)	O5—N1—C8—C7	78.1 (3)
P1—O2—C1—C3	−100.2 (2)	O6—N1—C8—C7	−101.1 (3)
P1—O3—C4—C5	−132.8 (2)	O4—C7—C8—N1	51.7 (2)
P1—O3—C4—C6	107.1 (3)	C10—C7—C8—N1	−72.1 (2)
O1—P1—C7—O4	73.94 (14)	P1—C7—C8—N1	162.77 (16)
O2—P1—C7—O4	−160.59 (12)	O4—C7—C8—C9	173.70 (17)
O3—P1—C7—O4	−51.80 (13)	C10—C7—C8—C9	49.9 (2)
O1—P1—C7—C10	−165.33 (14)	P1—C7—C8—C9	−75.2 (2)
O2—P1—C7—C10	−39.85 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···O1i	0.84	1.90	2.7289 (19)	172

Symmetry codes: (i) −x+1, y+1/2, −z+3/2.